Detergent sulphonic acid and sulphate salts of certain amphoteric detergents



United States Patent DETERGENT SULPHONIC ACID AND SUL- PHATE SALTS OF CERTAIN AMPHOTERIC DETERGENTS Hans S. Mannheimer, New York, N. Y.

No Drawing. Application February 28, 1956, Serial No. 568,159

7 Claims. (Cl. 26ll-401) This invention relates to novel compositions and to methods for producing them. In one of its more specific aspects, the invention is directed to the method of making and to novel derivatives of metal salts of substituted amido, amino acids, to which I shall hereinafter refer to as amino acid metal salts.

Said amino acid metal salts have been found useful as detergent, foaming, wetting, emulgating, emulsifying and dispersing agents. They are surface active agents, and serve as excellent synthetic detergents, dye assistants and softeners in the textile and related fields.

Said amino acid metal salts, employed as starting materials in the practice of this invention, have the following general Formula I:

in Which R is an organic radical, which, if connected to a carboxyl group, provides a monocarboxylic acid, and said radical contains at least 4 carbon atoms and for most purposes is a hydrocarbon radical of 4-18 carbon atoms; R1 is hydrogen or an aliphatic hydrocarbon radical having 1-4 carbon atoms, such as CH3, C2H5, --CsH'1, and -C4H9 or any one of said radicals having one or more of the hydrogens thereof which has been hydroxy substituted, illustrative examples of which are C2H4OH, CH2CHOHCH3, --CHOHCHOHCH2OH or any one of said radicals, but of 2-4 carbon atoms and Whose hydrogens have been either unsubstituted or hydroxy substituted and having at least one ether (O) and/ or keto (--CO) linkage therein, illustrative examples of which are C2H4OCH3, C2H4OC2H4OH,

-C2H4-COC2H4OH, CH2OHCOC2H5; R2 is a hydrocarbon group having 1-4 carbon atoms, such as Cl-l2, C2H4-, -C3Hs and C4Hs, or any one of the aforesaid groups, any one or more of Whose hydrogens has been hydroxy substituted, illustrative examples of which are --CH2CHOHCH2, CHLZCHOHCHOHCHZ and such hydrocarbon groups, wherein one or more of the hydrogen atoms thereof have been hydroxy substituted, or any one of said groups, but of 2-4 carbon atoms and whose hydrogens have been either unsubstituted or hydroxy substituted and having at least one ether (O) and/ or keto (CO-) linkage therein; M is a metal and preferably an alkali metal and, for most purposes, is sodium or potassium.

Said amino acid metal salts may be produced in a number of different ways:

One of the methods which may be employed is to first react an hydroxy diamine with an organic acid in the molecular proportion of 1 to 1. When approximately 1 mole proportion of water of reaction has been formed and the acid number of the mass is zero, the reaction is terminated, and the resulting reaction mass under specific 2,781,384 Patented Feb. 12, 1957 and controlled conditions is reacted with a metal salt of a monohalomonocarboxylic acid to provide an amino acid metal salt defined in Formula I.

The organic acid reacted With said hydroxy diamine is one containing a single COOH group or any of the available anhydrides of said acids and by the term monoca-rboxylic organic acid as used herein, I mean to include both the acid and the anhydride thereof which I regard as the equivalent of the acid. These acids may be: the aliphatic open chain saturated or unsaturated fatty acids as well as said fatty acids containing hydroxy or keto groups and/ or other substitutents, such as aryl radicals, as for example, acids of the type of Twitchell fatty acids; cycloaliphatic carboxylic acids preferably containing no more than 4 condensed nuclei and examples of which are hexahydrobenzoic, resinic, and naphthenic acids; heterocyclic aliphatic carboxylic acids, such as the various pyridine carboxylic acids.

While carboxylic acids having any number of carbon atoms may be employed, I prefer to employ those having at least 5 carbon atoms and preferably 5-19 carbon atoms in straight chain relationship. The acids which I employ may be derived from a number of different sources. Among some of them are the acid components chosen from oil or fats of animal, marine or vegetable origin and these include; the acids of cocoanut, palm kernel and palm oil, also from soy bean, linseed, olive, rapeseed, cottonseed, peanut and castor oil which contain large proportions of unsaturated hydroxy fatty acids and also the acids derived from tallow, fish and seal oils, whale or shark oils and the hydrogenated acids from these sources. Moreover, the synthetic high molecular Weight fatty acids, obtained by the oxidation of parafiin wax and similar high molecular Weight hydrocarbons by means of gaseous oxidizing agents may be employed. In addition the acid may be one of the resinic acids, such as abietic acid, or the naphthenic acids and long chain fatty acids having an aromatic hydrocarbon radical connected directly with the aliphatic chain (TWitchell fatty acids) as are obtainable from oleic, ricinoleic, linoleic and similar unsaturated fatty acids. Instead of employing mixture of acids from oil, fats and resins, single acids may be used, for example, caproic, myristic, heptylic, caprylic, undecylic, lauric, palmitic, stearic, behenic, arachic, cerotic, oleic, erucic, linoleic, linolenic, ricinoleic and hydroxystearic acids.

Of the aforesaid hydroxy diamines I prefer to employ aminoethylethanolamine hereinafter referred to as reactant A. Because it is commercially available in large quantities, its use provides for eiiicient production of some of the starting materials.

Examples of some of the other hydroxy diamines which may be employed in the production of starting materials are methyl amino isopropyl isopropanol amine (CHsNI-ICsHsNI-ICsHsOl-I), amino isobutyl isobutanol amine (NHzCiHsNHCiHsOH), amino hydroxy-propyl propane diol amine, (NH2C3H5OHNHC3H4(OH)2), propyl amino ethoxy ethyl ethoxy ethanol amine (C3Ii'ZNHCflHeOC2H4NHC2H4OC2H4OH), butyl amino hydroxyl propyl acetol amine,

(C4H9NHC3H5OHNHCH2COCH2OH) ethyl amino propanone ethanol amine (C2H5NHCH2COCH2NHC2H4OH) respectively, hereinafter referred to as reactants B, C, D, E, F, and G.

The reactants A-G respectively may be produced by employing a number of different classical methods well known to the art. One method consists essentially in chloride of the R2 group between the two "nitrogens and has formula ClR2Cl, and subsequently treating the diamine produced with caustic soda to remove HCl which is attached. Then the resultant diamine is reacted with a compound of the formula Cl-Rz-OH, and if R1 is other than hydrogen, another reactant Ri-Cl is used. Again, the hydrochloride is removed. In this manner, the various hydroxy diamines employed in the production-of my starting materials may be produced and are of the following formula:

in which R and R2 have heretofore been defined.

One of the well-known commercial methods employed in the production of said diamines whose general formula is above set forth is predicated upon the reaction of epoxy compounds, such as, ethylene oxide, propylene oxide, etc., with ammonia to form the intermediate diamine, which is subsequently reacted with additional epoxy compound in the presence of water.

Among some of the salts of the halo acids which may be employed are the sodium and potassium salts of monochloracetic acid, monochlorpropionic acid, monochlorlactic acid, monochlorhydroxyacetic acid obtainable from dichloracetic acid, monochloracetoacetic acid, monochlorethoxyacetic acid, etc.

One of the general types of method which may be employed for the production of some of these starting materials consists in first reacting one mole of a monocarboxylic acid having at least 4 carbon atoms in its radical connected to its COOH group with one mole of one of said hydroxy diamines, examples of which are reactants A-G, until only approximately 1 mol of water has been removed. In carrying out this reaction the mixture is first heated to about l-180 C. in vacuum of 90-130 mm. of mercury pressure until one mol of water of reaction has been produced and removed. (All of the terms mm. and mm. pressure as used in this entire description are intended to mean mm. of mercury pressure.) The reaction mass is then allowed to cool to room temperature and is then at elevated temperatures reacted with a monohalocarboxylic acid in the presence of 4 mols' of caustic soda in aqueous solution. In one of its preferred forms one mol of said reaction mass is added to an aqueous solution containing two mols of the monohalocarboxylic and 4 mols of caustic soda, which solution prior to the addition has been prepared and maintained at a temperature no greater than C. The mix is heated to a temperature of 95 C. until the pH has been reduced from about 13 to 8-8.5 and there is no further change in pH upon continued heating at said temperature.

Another method which may be employed for producing some starting materials of Formula I in the practice of this invention is as follows:

The reaction mass of the monocarboxylic acid and the hydroxy diamine, an example of which is product X, is heated to 90100 C. and there is gradually added thereto a di-molecular proportion of monohalomonocarboxylic acid, such as monochloracetic acid, whereupon exothermic reaction occurs and the temperature rises from 90100 C. to about 130-l60 C. The resultant is allowed to cool to 100 C. and is then dissolved in water. To this solution is added an aqueous solution containing 2 mols of caustic soda for each mol of monochloracetic acid previously used. This mass is stirred for about minutes at a temperature of about 60 C. The resultant product is a reaction product as defined in Formula I.

Still another method which may be employed for the production of the intermediate, known herein as product X, is to react 1 mole of an acid chloride, having the general formula R--CO-Cl; R being heretofore defined,

' maintained at that temperature for 2 hours.

4 with one mole of the hydroxy diamine in the presence of water and caustic soda.

The following are illustrative examples given merely for the purposes of specifically illustrating how some of the starting materials employed in the practice of the present invention may be produced, all parts being given by weight unless otherwise specified.

EXAMPLE A 200 parts of lauric acid and 104 parts of reactant A are placed in a reacting vessel and are heated sufiiciently to melt the lauric acid whereupon an agitator located therein is started and mixes and maintains these components in mixed condition. While being constantly agitated the mix is heated under vacuum of about 110mm. pressure for about 3-4 hours while gradually raising the temperature to 160-170 C. During this period 18 parts of water have been formed and distilled ofi", leaving behind a reaction mass having an acid number of approximately zero. Then this reaction mass, herein known as product X, is allowed to cool to room temperature and the entire mass is added to a previously prepared solution produced by adding 192 parts of monochloracetic acid and 160 parts of caustic soda to 600 parts of water. This solution was prepared and maintained at a temperature below 20 C. before the addition of said reaction mass. This mixture is heated to 95 C. and maintained at this temperature for 2 hours. During this period the pH of the mix is reduced from approximately 13 to 23-85. At the endof this period the pH of this mass is no longer subject to change by continued heating at said temperature and a sample of the resulting product is water soluble to a sparkling clear solution. At the end of this period the mass consists chiefly of a water solution of one of my starting materials, hereinafter known as product A and having the following formula:

Employ the same procedure as that set forth in Example A, except that only 96 parts of monochloracetic acid, parts of caustic soda in 300 parts of water are used, and the resultant mass is essentially an aqueous solution of a product, herein known as product W, having the following formula:

To such aqueous solution containing 389 parts of said product W, there is added an aqueous solution consisting of 40 parts of caustic soda dissolved in 40 parts of water. Then to said mixture there are added 80.5 parts of ethylene chlorhydrin. This mixture which at this stage is at room temperature is heated over a period of 1 hour to C. The mass is subsequently maintained at this temperature of 95 C. until there is no change in pH, this taking approximately 2 to 3 hours. The reaction mass consists essentially of an aqueous solution of a product, hereinafter known as product W-1,'and having the formula which is the same as that of product W, except that C2H4-OC2H4-OH is substituted for C2H4-OH.

To the resultant solution containing approximately 400 parts of product W-l, cooled to room temperature, there is added a previously prepared solution produced by adding 96 parts of monochloracetic acid and 80 parts of caustic soda to 300 parts of water. This solution was prepared and maintained at a temperature below 20 C. before the addition of said aqueous solution of product W-l. This mixture is heated to 95 C. and During this period, the pH of the mix is reduced from approximately Moment 13- to 8-8.5. At the end of this period, the pH of this mass is no longer subject to change by continued heating at said temperature and a sample of the resultant product is water soluble to a clear solution. At the end of this period, the mass consists chiefly of a water solution of another of my starting materials, hereinafter known as product B, of the following formula:

021140 C2H4O CH C O ONa CnHn-C O-ll*-C2H4N CH GO ONa EXAMPLE C 172 parts of caproic acid and 104 parts of reactant A are heated and reacted under the same condition as given in Example A, and 240 parts of the reaction mass produced thereby are introduced into a solution of 220 parts of monochlorpropionic acid and 160 parts of caustic soda in 600 parts of water prepared and maintained below C. The resulting mixture is then heated under the same conditions as outlined in Example A until the resulting product forms sparkling clear aqueous solutions and is no longer subject to pH change in continued heating. At the end of this period the mass consists chiefly of an aqueous solution of one of my starting materials, hereinafter known as product C, and having the formula the same as product A, except that Col-I19 is substituted for C11H2: and Cal-l4 for each CH2 therein.

EXAMPLE I) 282 parts linseed fatty acid and 104 parts reactant A are treated in the same manner as described in Example A. The entire reaction mass is then processed with an aqueous solution of 192 parts monochloracetic acid and l'60 parts of caustic soda previously made and maintained below 20 C. and subsequently processed .in the manner of Example A to produce starting material, hereinafter known as product D, and having the same formula that of product A, except that (31717131 is substituted for Chi-I2 therein.

EXAMPLE E ll6 parts of caproio acid and 104 parts of reactant A are condensed in the manner as described in the previous examples and the resulting reaction mass is subsequently processed in the same manner as that set forth in the processing of that of Example A.

The reaction product has the same formula as that of Example A, except that Cal-I11 is substituted for CuHzs therein, and is hereinafter known as product E.

EXAMPLE F 284 parts of stearic acid and 104 parts of reactant A are heated in the like manner as described in previous examples, and the resulting reaction mass is then intro duced into an aqueous solution of 248 parts monochlorlactic acid and 160 parts of caustic soda. The process is carried out in the same manner as described in the Example A, and there is produced a product having the same formula as that of Example A, except that CrzHss .is substituted for CnHza, CHzCI-IOHCOONa is substituted for each Cri 1-COGNa therein, and is hereinafter known as product F.

EXAMPLE G 290 parts dodecyl benzo'ic acid and 104 parts of reactant A are condensed in the manner described in Example D and the resultant mass is processed in the manner of Example D, whereby there is produced a novel compound having the same formula as that of Example A, except that CiziissCsHt is substituted for Culizs therein, and is hereinafter known as product G.

EXAMPLE n 228 parts of myristic acid and 104 parts reactant A are reacted in the manner described in Example D and the resultant mass is processed in the manner of Example 1'), whereby there is produced a starting material hereinafter known as product H, and having the same formula as that of Example A, except that C13H27 is substituted for C11H23 therein.

Still another type of method may be employed to produce some of these compounds, and examples thereof are shown hereinafter merely in an illustrative and not in a limiting sense.

EXAMPLE I 1 mol of lauric fatty acid and 1 mol of ethylenediamine (NHzCzI-IsNHz) are added together and then heated in the presence or an inert solvent such as toluol in amounts sufficient to dissolve the same. This solution is maintained at a temperature of approximately 110 C. This heating is carried out under a condenser through which pass vapors which consist of some of the solvent and water of reaction as well as small amounts of unreacted amine. These products are caught in a collector from which the water of reaction is removed and the condensed toluol and collected amine are returned to the reacting vessel. The temperature of the mass is maintained at 110 C. under the aforesaid conditions until 0.9 mol of water is collected. Then a vacuum of approximately mm. of mercury is applied to the reacting vessel and the temperature maintained at C. until all of the solvent and an additional 0.1 mol of water have been removed. To the resulting mass is added 1 mol of monochloracetic acid and this mixture is heated to a temperature of approximately C., whereupon the temperature of the mass will spontaneously rise to C. By the application of external heat the mass is maintained at said temperature at approximately 170 C. until a one part sample thereof when dissolved in 100 parts of aqueous solution of sodium hydroxide having a pH of approximately 9 provides a clear solution. 1 mol of this mass so produced is added to an aqueous solution containing 1 mol of sodium hydroxide. The entire mass is heated to approximately 80 C. whereupon there is formed the sodium salt of said mass, having the following formula:

The aforesaid salt, whose structural formula is shown in this example may be produced in still another way. Instead of adding the monochloracetic acid at the stage previously shown, there first may be prepared an aqueous solution containing 2 mols of sodium hydroxide and one mol of monochloracetic acid. The temperature of this solution is reduced below 15 C. and preferably 5 to 10 C. and while maintained at said reduced temperature and being constantly agitated there is added thereto one mol of the lauric acid-ethylene diarnine reaction mass. While being constantly agitated, the temperature of the mass is raised over a one-hour period to about 95 C. Then the-temperature of this constantly agitated mass is maintained at 95 C. for an additional 3 hours or until a sample thereof in 100 parts of water will be clear and the pH is no longer subject to change on further heating of the mass at that temperature.

1 .mol of the last defined compound is added to a solution containing one mol of caustic soda and one mol of ethylene chlorhydrin dissolved in water at a temperature not exceeding 15 C. and preferably between 5 to 10 C. After the addition at said low temperature, the mass is continuously agitated and while in the state of agitation its temperature is raised over about a one hour period to 95 C. and is further continuously agitated and maintained at said temperature for an additional 3 hours, all of this being done under a reflux condenser. During said 3 hour period, the pH of the mass continuously decreases. At the expiration of that 4 hour period the pH of 1 partof the mass when dissolved in 100 parts of water will be 8.5. The 1 part sample when dissolved in 100 parts of water and having a pH of 8.5 in the water, provides a clear. solution of product of the following formula:

Said mass, being an aqueous solution containing approximately 365 parts of said compound, is cooled to room temperature. Then there is prepared at a tempera ture of to C. an aqueous solution consisting of 96 parts of monochloracetic acid and 80 parts of sodium hydroxide and 300 parts of water. While constantly maintaining said solution in said temperature range, and .While being constantly stirred, said aqueous solution of said compound is slowly added thereto. While being constantly agitated, the temperature of the mass is raised over a one-hour period to approximately 95 C. Then the temperature of this constantly agitated mass is kept at 95 C. for an additional 3 hours or until a sample thereof in 100 parts of water will be clear, and the pH is no longer subject to change on further heating of the mass at that temperature. The resultant product so produced is the same as product A heretofore identified in Example A.

Still another method for producing product A heretofore identified in Example A is to disperse 1 mole of C11H23-CONHC2H4-NH2 in water. Then there is added thereto 1 mole of ethylene chlorhydrin and 1 mole of caustic soda, and said mass is slowly heated over a period of about 1 hour until the temperature thereof reaches 100 C. Then the mass is maintained at said tem perature of 100 C. for 3 hours. At the end of this period when all of the ethylene chlorhydrin has been reacted, the resultant mass contains approximately 1 mole of which is the same as product X of Example A and may be reacted with 2 moles of monochloracetic acid and 4 moles of caustic soda in the manner shown in Example A to provide product A whose formula is shown therein.

EXAMPLE K EXAMPLE L By following the same procedure as that set forth in Example I with the only dijference being that one mol of pentaerythritol chlorhydrin (CH2ClC(CH2OH)3) is substituted for the mole of ethylene chlorhydrin there is produced another one of my starting materials, hereinafter known as product L, and having a formula the same as product A, except that cnzc rcrnon gcnzocrncooua is substituted for --C2H4OCHzCOONa thereof.

EXAMPLE M By following the same procedure as that set forth in Example I with the only difference being that one mol of dimethylhydroxy ketone chlorhydrin is employed instead of the one mol of ethylene chlorhydrin there is produced another one of my starting ma- 8 terials hereinafter known as product M, and having a formula the same as product A, except that CH2COCH2OCH2COONa is substituted for the'--C2H40CHzCOONa thereof. The ketone employed in this example may be prepared by employing the well-known method consisting essentially of the distillation of 2 mols of hydroxy acetic acid with one mol of calcium carbonate after which the ketone is chlorinated to provide the above reactant.

EXAMPLE N By following the same procedure as that set forth in Example I with the only difference being that, instead of employing one mol of ethylene chlorhydrin, there isemployed one mol of the following compound:

, ClCHzC OCH there is produced another one of my starting materials, hereinafter known as product N, and having the same formula as that of product A, except that CH2COCHOHOCH2COONa By following the same procedure as that set forth in Example A with the only difference being that 2 mols of monochlorlactic acid are employed instead of the 2 mols of monochloracetic acid so that there is produced still another of my starting materials, hereinafter known as product P, having the same formula as product A, except that CHzCHOHCOONa is substituted for CHzCOONa of product A.

' EXAMPLE Q Employing the same procedure as that set forth in Example A, except that 1 mol of capric acid and 1 mol of reactant B and 2 mols of monochlorproprionic acid are substituted for the lauric acid, reactant A and monochloracetic acid, so that there is produced a starting material, hereinafter known as product Q, having the following formula:

Employing the same procedure as that set forth in Example A, except that 1 mol of s-tearic acid, 1 mol of reactant C, and 2 mols of monochlorlactic acid are employed in place of the lauric acid, reactant A and monochloracetic acid, there is provided a starting material, hereinafter known as product R, having the following formula:

EXAMPLE s Employing the same procedure as that set forth in Example A, except that} mol of myris'tic acid, 1 mol of 9 reactant D and 4 mols of potassium hydroxide are used in place of the lauric acid, reactant A and caustic soda, to provide starting material, hereinafter known as product S, having the following formula:

H CHaCHOHCHa-O-CHr-COOK OiaH21-C O-fI-CHzCHOHCHz-N 0112-6 0K EXAMPLE T Employing the same procedure as that set forth in Example A, except that 1 mol of capric acid, 1 mol of reactant E, and 2 mols of monochlorethoxyacetic acid are used in place of the lau'rie" acid, reactant A- and monochloracetic acid to provide starting material, hereinafter known as product T, having the following formula:

Employing the same procedure as that set forth in Example T, except that 1 mol of oleic acid, 1 mol of reactant F and 2 mols of monochloracetoacetic acid in place of the lauric acid, reactant A and monochl'oracetic acid to provide starting material, hereinafter referred to as product U, having the following formula:

04H; CHzCOCHr-O-CHaCOCHzCOONa The specific monocarboxylic acids, as well as the specific monohalomonocarboxylic acids employed in certain examples, may be replaced by others as may be the various other reactants in the specific examples to provide a great number of other starting materials, which differ from those set forth in the examplesh'eret-ofore set forth.

Prior to this inventiomit Was known that cationic surface active agents and anionic'surface active agents when together in aqueous solution resulted in the production or formation of water insoluble compounds, andtha't adding an anionic surfaceactiveagent-to an aqueous solution of another anionic surface active agent resulted in a mere physical combination of said agents and that no reaction would occur between them.

Said amino acid metal salts normally behave anionically in aqueous solutions having a pH above 7, and consequently it was expected that said amino acid metal salts when in aqueous solution together with anionic surface agents that they would be combined physically only and that no chemical reaction wo ld'oeenr 'therebetween. In the course of my experimentations, I have discovered that said amino acid metal salts could'be reacted with certain anionic surface active agents at a pH above 7 to produce water-soluble reaction products. Not "only-did I make said discovery, but I further discovered that water solutions of such reaction products had viscosities greater than corresponding aqueous-solutions of the amine acid metal salts and also exhibited better foaming -characteristics than did said amino acid metal salts in very low dilutions under extreme water hardness conditions. Said reaction products are non-toxic "'zfnduioflifrifating to the' 10 human skin. They have been found eminently useful as general utility detergents, such as forcar washing, dish washing, clothes washing, etc; Said amino acid metal salts" when used as components of shampoos sometimes caused slight irritation or stinging of the eyes when such shampoos were used and water solutions thereof acciden-tally reached the eyes. I have further discovered that the reaction products of this invention caused practically no irritation or stinging of the eyes when so employed.

According to this invention, one or a combination of two or more of said amino acid metal salts of the general structural Formula I are reacted with one or a combination of two or more anionic surface active agents of the following general structural Formula II to provide novel, water-soluble compounds having the following general structural Formula III, and having high wetting, detergency and surface active properties and capable of providing voluminous and stablefoams in aqueous solutions, and which aqueous solutions are substantially nonir'ritating to the skin and eyes of normal human beings.

wherein R3 is a hydrocarbon radical, generally aliphatic or aliphatic-aromatic, and having at least 6 carbon atoms and for most purposes 6-20 carbon atoms; Z is either oxygen or sulphur; and x is an integer and being at least 1 and generally 15, and preferably 3; M, R, R1 and R2 have heretofore been definedin Formula I.

According to this invention, I react a compound of Formula I with a compound of Formula II to provide the novel and highly useful compounds of Formula III. In general, this reaction is carried out in a solution containing compounds I and II and to which a quantity of an acidic agent such as a strong mineral acid, as for example hydrochloric, sulphuric or its equivalent, has been added to lower the pH of the solution to a value of approximately 7 to approximately 9 and while maintaining the mass at a temperature between approximately 200 F. In this reaction under the aforesaid conditions, the compounds of Formula III are produced, said compounds having high water solubility in spite of the fact that the number of carbon atoms in R3 is 6 or more. Such compounds of Formula III have an unexpected extremely high water-solubility, while the corresponding salts of cationic compounds are water-insoluble. T he resultant aqueous solution can be used directly as a surface active agent, wetting agent or detergent for the pur poses indicated for the amino acid metal salts. While the quantities of the compound of Formula I and com pound of Formula II may be equimolecular for good yield of compounds of Formula III, I may employ an excess of either, and in general the mole ratio of a cornpound of Formula I to compound of Formula II may be 2 moles of the former to l3 moles of the latter.

One of the specific methods which I prefer to employ in carrying out an aspect of this invention is to first dissolve a compound of Formula I in water and then the pH thereof is adjusted to approximately 12-13 (measured electrically) by the addition of aqueous caustic soda if required so that when a compound or Formula II is added thereto, the pH of the solution of I and II will be at least 10 and generally -11. The temperature of said solution is raised to IOU-200 F. and preferably in factory practice to'approximately P. Then a quantity of a compound'of-fiormula II is dissolved in water in a separate container and this solution is added to said first solution and the mass is maintained in said temperature range 11 while being constantly stirred, and an acidic agent is added thereto to reduce the pH thereof to a value below and in the range of approximately 7 to 9,,and preferably of approximately 8.2 to approximately 8.7. At the end of the acidic agent addition, the stirring is continued and the temperature of the mass maintained for about 10-20 minutes after which the solution is allowed to cool and is a finished product.

The following are specific examples merely given by way of illustrating the invention and are not to be taken by way of limitation, all parts being given by weight unless otherwise specified.

EXAMPLE 1 An aqueous solution of 500 parts of product A in 750 parts of water is heated to approximately 140 F. and its pH (measured electrically) is adjusted by the addition of aqueous caustic soda to 12-13. While being constantly stirred and maintained at that temperature, there is added a solution of 400 parts of sodium salt of lauryldiethoxyether sulfate:

in 600 parts of water. Then while stirring and the temperature is maintained, there is added thereto between about 3040 parts of hydrochloric acid solution (32%), whereby the pH of the mass is lowered to a value in the range of 8.2 to 8.7. Stirring is continued and the temperature maintained for about 10 minutes more. The resultant product is a solution of the novel reaction product, having the following formula:

EXAMPLE 2 Employ the same procedure and components as set forth in Example 1, except that only about 200 parts of the sodium salt of lauryldiethoxyether sulfate are used. In this instance, the resultant product is a solution of the novel reaction product whose structural formula is shown in Example 1 together with unreacted product A used, in the approximate proportion of two parts of the former to one of the latter.

Employ the same procedure as that set forth in Example l, but employ the components indicated in the following Examples 3-36; the quantity of hydrochloric acid solution (32%) is variable to lower the pH to values indicated in Example 1 to obtain the novel reaction products of said Examples 3-36.

EXAMPLE 3 FORMULA OF NOVEL REACTION PRODUCT C2H4-O-CH -COON3 450 parts of product C in 700 parts of water. parts of tridecyl tetraethoxyether sulfate sodium salt:

C13H27-O- Cal-I40 4SO3-Na in 750 parts of water.

500 parts of product A in 750 parts of water. 500 parts of nonylphenoltriethoxyether sulfate sodium salt:

CsH19-C6H4-O( Cal-I40 aSO3 in 750 parts of water.

FORMULA OF NOVEL REACTION PRODUCT CaHt-O-CHr-C O 0N9.

500 parts of product Q in 800 parts of water. parts of hexylrnonoethoxyether sulfate sodium salt:

CsI-I1a--O(CzH4O)SO3-Na in 400 parts of water.

FORMULA OF NOVEL REACTION PRODUCT OH: CH; OHg-GH-O-CzH4OOONa CgHmCOi ICHg( JHN OHa H CzHi-COONa CeHn-O(C:H40)S0t EXAMPLE 7 660 parts of product R in 1,000 parts of water. 600 parts of stearoylpentethoxy thioether sulfate sodium salt:

parts of octylphenol diethoxy thioether sulfate potassium salt:

CzHt-C O ONa CHaCHOHGOONa CsH17Csl-I4-S-(C2H40)aSO3-K in 500 parts of water.

FORMULA OF NOVEL REACTION PRODUCT H OHzCHOHCHz-O-OHa-OOONa CisHz7-C 0I TCHaCHOHGH7-N H CHTCOOK CGHIPCOHPS-(CQH4O)I SO3 EXAMPLE 9 575 parts of product T in 900 parts of water. 400 parts of decyltriethoxy thioether sulfate sodium salt:

C1oHa1S(C2H4O)3SO3Na in 600 parts of water.

FORMULA OF NOVEL REACTION PRODUCT 0:111 CIHiO Gilli-04321140 0112-0 0 ONa Collie-C O-N-C B AO CzHt-N .13. EXAMFLE 10 675 parts of product U in 1,000 parts of water. 500 parts of amylphenylpentaethoxyether sulfate sodium salt:

CH11C6H40-(C2H40) s--SOa-Na in 750 parts of water.

FORMULA OF NOVEL REAGTIO'N PRODUCT C4H9 CHCOCHz-O-CHz-CO-CHz-COONa CHHM'OO-N-OHZGHOHOHTN H CEzOOCHz-COONa C5H11C6H4"O(C:H4O)5SO3 EXAMPLE 11 650 parts of product V in LOGO parts of water. 500 parts of tridecyltetraet hoxy thioether sulfate potassium salt:

Cia'H2rS-( Cal-I40 4-SOa-K in 750 parts of water.

FORMULA OF NOVEL REACTION PRODUCT 02113 CzH4OCHzCOOK n crn-ooon cnnn-soznron-s o EXAMPLES 12-1-6 Employing the same procedure as that set forth in Example 1, except that products B, K, L, M, and N are respectively substituted for product A to provide other novel reaction products.

EXAMPLES 17-20 Employing the same procedure as that set forth in Example, 1 except that products D, E, G, and H are respectively substituted for product A to provide novel reaction products, which differ from the novel reaction product whose formula is shown in Example 1, by substituting for the CrrHzs radical thereof the following respective radicals: C17H31, CsHn, C12H25-C6H4 and C13H27.

EXAMPLE 21 Employing the same procedure as that set forth in Example 1, except that product P is substituted for product A to provide a reaction product which differs from the novel reaction product, whose formula is shown in Example 1, by substituting for the CH2COONa radical the following radical: CH2CHOHCOONa.

EXAMPLES 22 AND 23 Employing the same procedure as that set forth in Example, except that products C and F respectively are substituted for product A to provide novel reaction products which ditfer from the novel reaction product whose formula is shown in Example 1, by substituting C2H4COONa for the CH2COONa and also substituting C9H19 and CrzHss respectively for C11H23.

EXAMPLES 24-36 Employing the same procedure as that set forth in Example 3, except that, instead of product A, there are respectively substituted compounds which are the same as product A, except that the H of the NH attached directly to the CO group thereof is replaced by the following respective radicals: CHs, CH2H5, -C3H7,

C4H9, -C2H4OH, CH2CHOHCH2, -CHOIICHOHCH2OH, -C2H4OCI-Is, -C2H4OC2H4OH, -CH2CHOHOC2H5, -CH2COCH3, -C2HCOC2H4OH, CH2OHCOC2H5; whereby there are produced a number of other novel reaction products whose formulas are the same as the formula of the novel reaction product whose formula is within the definition of Formula H1 and shown in Example 3, except that the CTl 14 aforesaid respective radicals replace the H of the NH connected directly to the CO thereof.

Following the same procedure as that set forth in Ex ample 1 and employing 1 mol of any of said other starting materials of Formula I respectively, and 1 mol of any of the other specific compounds of Formula II employed in Examples 1-3 6, a great number of other novel reaction products whose formulas are that of Formula III may be produced; and in addition, the specific reactants employed may differ from those employed herein, in varying R, R1, R2 and Rs within the definitions thereof, to provide a great number of other compounds of Formula III.

It is to be understood that instead of first adjusting the pH of the compound of Formula I to 12-13 before the addition of the compound of Formula II, any other method may be employed to obtain the condition whereby the pH of the solution of I and II is at least 10 and preferably 10.5-11 before the addition of the acidic agent to lower the pH of the mass to approximately 7 to approximately 9. For example, I and II may be dissolved together and this solution may, by the addition of caustic soda when required, have its pH adjusted to at least 10, and then at -200 F. is ready for the addition of the acidic agent to lower its pH to approximately 7 to approximately 9. If desired, the required amount of acidic agent may be added either before or after the solution of pH of at least 10 is brought to a temperature in the range of 100200 F.

Since certain changes in carrying out the aforesaid processes and certain modifications in the compositions which embody the invention may be made without departing from its scope, it is intended that all matter contained in the description shall be interpreted as illustrative and not in a limiting sense.

It is also to be understood that the following claims are intended to cover all the generic and specific features of the invention herein described, and all statements of the scope of the invention which as a matter of language might be said to fall therebetween.

I claim:

1. A compound of the following formula:

in which R is a hydrocarbon radical of 4-18 carbon atoms; R2 is an organic group selected from the class consisting of (a) aliphatic hydrocarbon groups of 1-4 carbon atoms; (b) hydroxy substituted aliphatic hydrocarbon groups of 1-4 carbon atoms, (c) aliphatic ether groups, each of said ether groups having at least one other oxygen linkage therein and otherwise being hydrocarbon of 2-4 carbon atoms, (d) aliphatic ether groups, each of said groups having at least one ether oxygen linkage therein and otherwise being hydroxy substituted hydro-carbon of 2-4 carbon atoms, (e) aliphatic keto groups, each of said groups having at least one carbonyl linkage therein and otherwise being hydrocarbon of 2-4 carbon atoms, (7) aliphatic keto groups, with each of said groups having at least one carbonyl linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-4 carbon atoms, (g) aliphatic groups having keto carbonyl and ether oxygen linkages therein, and otherwise being hydrocarbon of 3-4 carbon atoms, (h) aliphatic groups, each of said groups having keto carbonyl and ether oxygen linkages therein and otherwis being hydroxy substituted hydrocarbon of 3-4 carbon atoms; R1 is selected from the group consisting of hydrogen and monovalent radicals otherwise defined .in said (a)-(h); R3 is a hydrocarbon radical selected from the class consisting of aliphatic and aliphatic-aromatic hydrogen radicals of 6- 20 carbon atoms; x is 1-5; Z is selected from the group 1 5 1 6 consisting of oxygen and sulphur; and M is an alkali in which R3 is a hydrocarbon radical of 6-20 carbon atoms metal. 7 and x is 1-5.

2. A compound of the following formula: 5. A compound of the following formula:

I 021140 CHT-GOONH Ell ClHL-OCH2-'COONB RC O-N-C 2H4N 5 C 1123-0 O-NC2H4N H GHQ-000M H 0112-0001 in which R is an aliphatic hydrocarbon radical of 4-18 in which R3 is a hydrocarbon radical of 620 carbon carbon atoms and R3 is an aliphatic hydrocarbon radical 0 atoms and x is 1-5.

of 62() carbon atoms, and x is 1-5. 6, A compound of the following formula:

3. A compound of the following formula: (3QH4 O CHB OOONa Ell CzHtQ 0112-0 0 ONE; CuH23 C q 7 RCON--C:H47N\ 7 15 n J oar-000m H CHQ-OOONR O Oz Ra-S(C2H40):S0s in which R is an aliphatic hydrocarbon radical of 4-18 Awmpound of the followmg formula: carbon atoms and R3 is an aliphatic hydrocarbon radical 20 H C2H4-OCH:CO0Na of 6-20 carbon atoms, and x is 1 5. CXHPO 1 4. A compound of the following formula:

H CHa-C O O Na CgH4O-CH2C 0 ONE. L C12H25-O(C2H4O)a-30a C 11 2sC O-1\CgH4-N 26 V H gH C References Cited in the file of this patent R3-0(01H40)z 03 UNITED STATES PATENTS 2,103,872 Schoeller Dec. 28, 1937 2,329,406 Mauersberger Sept. 14, 1943 

1. A COMPOUND OF THE FOLLOWING FORMULA: 